US3959385A - Production of alcohols and/or aldehydes - Google Patents

Production of alcohols and/or aldehydes Download PDF

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Publication number
US3959385A
US3959385A US05/081,168 US8116870A US3959385A US 3959385 A US3959385 A US 3959385A US 8116870 A US8116870 A US 8116870A US 3959385 A US3959385 A US 3959385A
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US
United States
Prior art keywords
stands
phosphine
sub
trisubstituted organic
reaction
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Expired - Lifetime
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US05/081,168
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English (en)
Inventor
Hans Juergen Nienburg
Wilhelm Kniese
Rudolf Kummer
Peter Tavs
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BASF SE
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Badische Anilin and Sodafabrik AG
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Priority claimed from DE19691955828 external-priority patent/DE1955828C2/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5004—Acyclic saturated phosphines

Definitions

  • the invention relates to an improved process for the production of aldehydes and/or alcohols by the oxo process comprising the reaction of olefinically unsaturated compounds with carbon monoxide and hydrogen in the presence of carbonyl complexes of metals in Group VIII of the Periodic Table modified by trisubstituted organic phosphines.
  • olefinically unsaturated compounds of up to 20 carbon atoms, in particular of up to 16 carbon atoms.
  • the preferred olefinically unsaturated compounds may contain a number of double bonds, for example two nonconjugated double bonds or substituents which are inert under the conditions of the reaction, such as alkoxy of from 1 to 4 carbon atoms, carboxyl, carbalkoxy of from 2 to 9 carbon atoms, acyloxy derived from fatty acids, cycloalkane carboxylic acids or aromatic acids of up to 16 carbon atoms, or hydroxyl.
  • THe particularly preferred starting materials are olefinically unsaturated compounds of hydrocarbon structure.
  • olefins of from 2 to 20, especially of from 2 to 16, carbon atoms, in particular those having terminal double bonds are, for example, ethylene, propylene, hexene-1, octene-1, decene-1, cyclohexene, styrene, propenylbenzene, allyl alcohol, allyl methyl ether, methyl crotonate, methyl acrylate, olefin mixtures such as are from the oligomerization of propene and butene, such as so-called trimeric propylene or codibutylene and butene-3,4-diol-1,2-diacetate.
  • Carbon monoxide and hydrogen are generally used in proportions by volume of from 1:1 to 1:10, in particular from 1:1 to 1:3.
  • the olefinically unsaturated compounds may be used in stoichiometric amounts based on the mixture of carbon monoxide and hydrogen, but it is advantageous to use the said gas mixture in excess of the stoichiometric amount. It is even possible to use considerably more than the stoichiometric excess, for example up to 500% excess.
  • the reaction is advantageously carried out at temperatures rangingg from 140° to 250°C. Particularly good results are obtained when temperatures of from 190° to 230°C are used. Good results are obtained when the reaction is carried out under pressures of from, say, 20 to 350 atmospheres. It is advantageous to use pressures of from 30 to 80 atmospheres.
  • reaction is generally carried out in the presence of solvents which are inert under the conditions of the reaction, for example hydrocarbons such as cyclohexane or xylene, and alcohols such as butanol or aldehydes such as butyraldehyde.
  • solvents which are inert under the conditions of the reaction, for example hydrocarbons such as cyclohexane or xylene, and alcohols such as butanol or aldehydes such as butyraldehyde.
  • the reaction is carried out in the presence of carbonyl complexes of metals in Group VIII of the Periodic Table, which are modified by trisubstituted organic phosphines containing one or more carboxylic acid groups, at least one of which is in the form of its alkali or alkaline earth metal salt.
  • Preferred carbonyl complexes of metals in Group VIII of the Periodic Table are those of cobalt or rhodium. Cobalt carbonyl complexes have been found to be particularly useful commercially.
  • Preferred catalysts contain metal and phosphorus in an atomic ratio of from 1:1 to 1:4, in particular from 1:1 to 1:2.
  • the tertiary organic phosphines used as modifying agents generally have the same or different aliphatic, cycloaliphatic, araliphatic or aromatic radicals, of which at least one contains a carboxylic group. It is possible, however, for a number of carboxyl groups, say up to 4 carboxyl groups, to be present in the tertiary phosphine molecule. It is further possible for the phosphorus atom to form part of a heterocyclic ring, for example a 5 or 6 membered heterocyclic ring, and for the heterocyclic ring or the third substituted to contain one or more carboxyl groups.
  • Preferred tertiary organic phosphines have same or different aliphatic radicals of up to 20 carbon atoms, cycloaliphatic radicals of from 5 to 12 carbon atoms, araliphatic radicals of from 7 to 14 carbon atoms, or aromatic radicals of from 6 to 12 carbon atoms.
  • the most preferred tertiary phosphines are those in which the radicals containg said number of carbon atoms have, apart from the carboxyl groups or groups contained therein, hydrocarbon structure.
  • modifying agents consisting of tertiary organic phosphines of the general formula
  • R stands for alkyl of from 1 to 25 carbon atoms, cyclohexyl, phenyl, benzyl or, preferably, methyl,
  • Me stands for an alkali or alkaline earth cation, in particular sodium or potassium, in at least a stoichiometric amount for a carboxyl group,
  • n stands for an integer of from 1 to 14 inclusive, in particular from 8 to 14,
  • n stands for 1 to 3 inclusive, in particular for 1, and
  • p stands for 3-n, in particular for 2.
  • Suitable tertiary organic phosphines are, for example, bis-2-carboxyethyldodecyl phosphine, bis-2-carboxyethylphenyl phosphine, 2-carboxyethyldiphenyl phosphine, 10-carboxydecyldimethyl phosphine, 9(10'-carboxydecyl)-9-phosphabicyclo(4,2,1)-nonane, 9-(10'-carboxydecyl)-9-phosphabicyclo(3,3,1)-nonane, 9-n-dodecyl-9-phosphabicyclo (4,2,1)-nonane-3,4,7,8-tetracarboxylic acid, 9-n-dodecyl-9-phosphabicyclo-(3,3,1)-nonane-2,3,6,7-tetracarboxylic acid, 9-n-octyl-9
  • catalysts we prefer to use from 0.1 to 2% by weight of the said catalysts, calculated as catalyst metal based on the amount olefinically unsaturated compounds used. We have found amounts ranging from 0.2 to 1% by weight to be particularly convenient. It is possible to use preformed catalysts in the oxo reaction or alternatively, the starting materials for the catalysts may be added to the reaction separately or as partly preformed components. For example the esters of the phosphinic carboxylic acids or the free carboxylic acids themselves may be included in the reaction mixture and then converted to the desired salt in the reaction zone by the addition of the stoichiometric amount of alkali solution. The catalyst then forms automatically under the conditions of the reaction.
  • the process of the invention is carried out, for example, by passing olefins, a mixture of carbon monoxide and hydrogen and catalyst of the stated composition, optionally together with a suitable solvent, to the bottom of a vertical high-pressure tube in the desired proportions, and effecting the reaction under the stated conditions of temperature and pressure.
  • reaction mixture After the pressure has been released the reaction mixture is separated from the non-volatile and thermally stable catalyst by distillation, the catalyst remaining in the liquor at the bottom of the tube to be re-used as catalyst.
  • the aldehydes and alcohols produced by the process of the invention are valuable for the production of solvents and plasticizers for polymers and also in the production of detergents.
  • a high-pressure vessel of a capacity of 1,700 parts by volume is charged with 100 parts of butanol and 100 parts of octene, a mixture of carbon monoxide and hydrogen in the proportions of 1:1 by volume then being introduced under pressure.
  • the content of the tube are then heated to 180°C until a final pressure of 80 atmospheres gauge is reached.
  • the pressure during the reaction is maintained at 80 atmospheres gauge by continuously introducing fresh gas mixture under pressure.
  • Example 1 is repeated except that 9.2 parts of 10-carboxydecyldiethyl phosphine in the form of its potassium salt are used. After the reaction has proceeded for 2 hours, 39.5% of the octene is still unconverted. The mixture also contains 4.0% of octane, 4.2% of isononanol, 36.6% of n-nonanol, 3.3% of iso-nonanal and 12.4% of n-nonanal. The content of normal compounds is 87%.
  • Example 1 is repeated except that 11.8 parts of ⁇ -carboxyethyl ⁇ -carbethoxyethyldodecyl phosphine are used in the form of the potassium salt. After the reaction has proceeded for 2 hours, 38.9% of the octene is still unconverted. The mixture also contains 4.2% of octane, 6.1% of iso-nonanol, 35.4% of n-nonanol, 3.3% of iso-nonanal and 12.0% of n-nonanal. The content of normal compounds is 83%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US05/081,168 1969-11-06 1970-10-15 Production of alcohols and/or aldehydes Expired - Lifetime US3959385A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19691955828 DE1955828C2 (de) 1969-11-06 Verfahren zur Herstellung von Alkoholen und Aldehyden
DT1955828 1969-11-06

Publications (1)

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US3959385A true US3959385A (en) 1976-05-25

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US (1) US3959385A (ja)
JP (1) JPS4915244B1 (ja)
AT (1) AT301512B (ja)
BE (1) BE758502A (ja)
ES (1) ES385267A1 (ja)
FR (1) FR2069063A5 (ja)
GB (1) GB1320036A (ja)
NL (1) NL7015889A (ja)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248802A (en) * 1975-06-20 1981-02-03 Rhone-Poulenc Industries Catalytic hydroformylation of olefins
US4439625A (en) * 1982-09-29 1984-03-27 E. I. Du Pont De Nemours And Company Production of formaldehyde
US4716250A (en) * 1986-07-10 1987-12-29 Union Carbide Corporation Hydroformylation using low volatile/organic soluble phosphine ligands
US4731486A (en) * 1986-11-18 1988-03-15 Union Carbide Corporation Hydroformylation using low volatile phosphine ligands
EP0350921A1 (en) * 1988-07-14 1990-01-17 Union Carbide Chemicals And Plastics Company, Inc. Process for producing alcohols and aldehydes
US4945185A (en) * 1987-12-24 1990-07-31 Union Carbide Chemicals And Plastics Company Inc. Process for producing mixtures of ketones and aldehydes
US5180854A (en) * 1988-07-14 1993-01-19 Union Carbide Chemicals & Plastics Technology Corporation Process for catalyst aldehyde product separation
US5990358A (en) * 1996-02-13 1999-11-23 Basf Aktiengesellschaft Process for the preparation of formaldehyde

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60193995U (ja) * 1984-06-01 1985-12-24 河口株式会社 伸縮テ−プ
JPS6150782U (ja) * 1984-09-07 1986-04-05

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239569A (en) * 1960-07-22 1966-03-08 Shell Oil Co Hydroformylation of olefins
US3274263A (en) * 1961-08-30 1966-09-20 Shell Oil Co Process for olefin hydroformylation
US3400163A (en) * 1965-06-30 1968-09-03 Shell Oil Co Bicyclic heterocyclic sec- and tert-phosphines
GB1206063A (en) * 1967-10-24 1970-09-23 Montedison Spa Hydroformylation of olefins
US3646079A (en) * 1968-02-07 1972-02-29 British Petroleum Co Preparation of rhodium complexes
US3681465A (en) * 1967-11-07 1972-08-01 Ruhrchemie Ag Process of producing aldehydes using a catalyst including a group viii metal and phosphorus

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239569A (en) * 1960-07-22 1966-03-08 Shell Oil Co Hydroformylation of olefins
US3274263A (en) * 1961-08-30 1966-09-20 Shell Oil Co Process for olefin hydroformylation
US3400163A (en) * 1965-06-30 1968-09-03 Shell Oil Co Bicyclic heterocyclic sec- and tert-phosphines
GB1206063A (en) * 1967-10-24 1970-09-23 Montedison Spa Hydroformylation of olefins
US3681465A (en) * 1967-11-07 1972-08-01 Ruhrchemie Ag Process of producing aldehydes using a catalyst including a group viii metal and phosphorus
US3646079A (en) * 1968-02-07 1972-02-29 British Petroleum Co Preparation of rhodium complexes

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248802A (en) * 1975-06-20 1981-02-03 Rhone-Poulenc Industries Catalytic hydroformylation of olefins
USRE31812E (en) * 1975-06-20 1985-01-22 Rhone-Poulenc Industries Catalytic hydroformylation of olefins
US4439625A (en) * 1982-09-29 1984-03-27 E. I. Du Pont De Nemours And Company Production of formaldehyde
US4716250A (en) * 1986-07-10 1987-12-29 Union Carbide Corporation Hydroformylation using low volatile/organic soluble phosphine ligands
US4731486A (en) * 1986-11-18 1988-03-15 Union Carbide Corporation Hydroformylation using low volatile phosphine ligands
US4945185A (en) * 1987-12-24 1990-07-31 Union Carbide Chemicals And Plastics Company Inc. Process for producing mixtures of ketones and aldehydes
EP0350921A1 (en) * 1988-07-14 1990-01-17 Union Carbide Chemicals And Plastics Company, Inc. Process for producing alcohols and aldehydes
US5180854A (en) * 1988-07-14 1993-01-19 Union Carbide Chemicals & Plastics Technology Corporation Process for catalyst aldehyde product separation
US5990358A (en) * 1996-02-13 1999-11-23 Basf Aktiengesellschaft Process for the preparation of formaldehyde

Also Published As

Publication number Publication date
FR2069063A5 (ja) 1971-09-03
ES385267A1 (es) 1973-04-01
GB1320036A (en) 1973-06-13
AT301512B (de) 1972-09-11
BE758502A (fr) 1971-05-05
JPS4915244B1 (ja) 1974-04-13
NL7015889A (ja) 1971-05-10
DE1955828B1 (de) 1971-04-08

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